Benzothiazole azo cyclohexanedione-1, 3 compounds



BENZOTHIAZOLE AZO CYCLOHEXANEDIONE-1,3 COMPOUNDS JamesM. Straley,Kingsport, Tenn., and John Sagal, in,

Rochester, N. Y., assignors to Eastman Kodak Com- .pany, Rochester, N.Y., a corporation of New Jersey No Drawing. Application October 1, 1954Serial No. 459,824

Claims. (Cl. 260146) wherein Ar represents an ortho-arylene radical ofthe benzene series and X represents the radical of acyclohexanedione-l,3 compound joined through the carbon atom in its2-positionto the azo bond shown. The metallized azo compounds of ourinvention comprise the monoazo compounds having the Formula I in complexcombina-,

tion with chromium, cobalt, copper, iron, manganese, nickel andvanadium. The manner of preparing the nonmetallized and metallized azocompounds of our invention is fully described'hereinafter.

While our invention relates broadly to the non-metallized and themetallized monoazo compounds just described, the azo compounds of ourinvention are represented for the most part by the non-metallized andthe metallized forms of the azo compounds having the formula:

wherein Ar represents an orthov-arylene radical of the benzene series, Qrepresents a hydrogen atom, amethoxy group, an ethoxy group, a cyanogroup, a carbomethoxy group or acarboethoxy group and R and R reachrepresents a hydrogen atom, a methyl group or an ethyl group. 7

As is well known, one of the disadvantages dyed cellulose acetatetextile fabrics suffer in comparison with some of the dyed competingtextile fabrics, such as cotton, wool and viscose, for example, is lackof fastness to washing. Many schemes have been proposed to remedy thissituation but all suffer from some significant fault. By means of ourinvention dyed cellulose acetate textile materials having good toexcellent fastness to washing, light r 2,822,359 Patented Feb. 4, 1958"Ice and gas are obtainable. These results may be obtained by dyeing thecellulose acetate textile material withthe nonmetalized dye compounds ofthe invention and then treating the dyed cellulose acetate textilematerial with suitable metal salts which cause the original dye to formmetallic complexes which are resistant, for example, to the action ofwashing, light and gas. Thus, by means of the present invention, thedisadvantage noted above with respect to the wash fastness of dyedcellulose acetate textile materials is either entirely or largelyovercome.

While reference has been made to the dyeing of cellulose acetate textilematerials, it is to be understood that the invention is generallyapplicable to the dyeing of textile materials made of or containing acellulose alkyl carboxylic acid ester having two to four carbon atoms inthe acid groups thereof. By cellulose alkyl carboxylic acid estershaving two to four carbon atoms in the acid groups thereof, wemean toinclude, for example, both hydrolyzed and unhydrolyzed celluloseacetate, cellulose propionate, cellulose .butyrate, celluloseacetate-propionate and cellulose .acetate-butyrate. Cellulose acetatehas been particularly referred to because it is the most widely usedcellulose alkyl carboxylic acid ester,

The non-metallized monoazo compounds of our invention are prepared bydiazotizing a Z-aminobenzothiazole compound having the formula:

wherein Ar represents an ortho-arylene radical of the benzene series andcoupling the diazonium compound obtained with a cyclohexanedione-l,3compound.

The metallized monoazo compounds of ourinvention are prepared bytreating the non-metallized azo compounds having the Formula I withsalts of nickel, cobalt, copper, chromium, manganese, iron or vanadium.The non-metallized monoazo compounds can be metallized either on or olfthe fiber. Metallization can be carried out, for example, by treatingthe non-metallized dye with a solution or dispersion of the metallizingagent. Although the metal complex is often forrned at room temperature,we prefer to accelerate the process by heating, usually with steam, fora short time. The preparation of the metallized monoazo compounds of ourinvention is fully described hereinafter.

Illustrative of the metallizing agents that can be employed are thehalides, the sulfates, the acetates, the cyanides, and the thiocyanatesof nickel, cobalt, copper, chromium, manganese, iron and vanadium.Thu-s, .nickel chloride, nickel bromide, nickel sulfate, nickel acetate,nickel cyanide, nickel formate, nickel thiocyanate [Ni(SCN) cobaltousbromide, cobaltic chloride, co-

baltous chloride, cobaltous acetate, cobaltous cyanide,

ferric chloride, ferric fluoride, ferrousacetate, ferrous thiocyanate[Fe(SCN)zl ferric thiocyanate [Fe(SCN) and vanadium thiocyanate,areillustrative of the metalliz- A ing agents that can be employed.

When the metal complex is formed on a cellulose alkyl carboxylic acidester, such as cellulose acetate, fiber the use of a metal thiocyanateappears to be advantageous and is preferred. Nickel thiocyanate appearsto be especially useful and particular claim is laid to its use. Next tonickel thiocyanate the use of cobalt thiocyanate is preferred.

2 amino 6 methylsulfonylbenzothiazole, 2 amino 6ethylsulfonylbenzothiazole, 2 amino-- 6 n propylsulfonylbenzothiazole, 2amino 6 n butylsulfonylbenzothiazole, 2 aminobenzothiazole 6 N methylsulfonamide, 2 aminobenzothiazole 6 N ethylsul fonamide, 2aminobenzothiazole 6 N n propylsulfonarnide, 2 aminobenzothiazole 6 l nbutylsulfonamide, 2 amino 6 methoxybenzothiazole, 2 amino 6ethoxybenzothiazole, 2 amino 6 n L pro poxybenzothiazole, 2 amino 6 nbutoxybenzothiazole, 2 amino 6 methylbenzothiazole, 2 amino 6ethylbenzothiazole, 2 amino 6 n propylbenzothiazole, 2 amino 6 nbutylbenzothiazole, 2 amino 6 {3 hydroxyethylbenzothiazole, 2 amino 6 'y--hydroxypropylbenzothiazole, 2 amino 6 6 hydroxybutylbenzothiazole, 2amino 6 acetylaminobenzothiazole, 2 amino 6 npropionylaminobenzothiazole, 2 amino 6 n butyrylaminobenzothiazole, 2amino 6 thiomethylbenzothiazole, 2 amino 6 thiocyanobenzothiazole, 2amino 6 cyanobenzothiazole, 2 amino 6 trifiuoromethylbenzothiaozle, 2amino 6 chlorobenzothiazole, 2 amino 6 nitrobenzothiazole, 2 amino 4,7dimethoxybenzothiazole, 2 amino 5,6 dimethoxybenzothiazole, 2 amino 4,7diethoxybenzothiazole, and 2 amino 4,6 dimethylbenzothiazole arerepresentative of the 2-aminobenzothiazole compounds used in thepreparation of the azo compounds of our invention.

Cyclohexanedione 1,3; 5-methylcyclohexanedione-l,3; 5ethylcyclohexanedione 1,3; 5,5-dimethylcyclohexane dime-1,3;5,S-diethylcyclohexanedione-1,3; 4-carbomethoxy 5,5-dimethylcyclohexanedione 1,3; 4-carboeth0xy-5,S-dimethylcyclohexanedione-1,3;4methoxy-5,5-dimethylcyclohexanedione-l,3; 4-ethoxy 5 ,5dimethylcyclohexanedione-1,3; 4-methyl-5,5-dimethylcyclohexanedione-l,3; 5 phenylcyclohexanedione 1,3; 4-phenyl-5-phenylcyclohexanedione 1,3;4-cyano-5-phenylcyclohexanedione-1,3; 4-cyano-6-methyl 5phenylcyclohexanedione-1,3; 5-cinnamyl-6-carboethoxycyclohexanedione1,3; 4-cyano-5,5- dimethylcyclohexanedione 1,3;4-cyano-5,S-diethylcyclohexanedione-1,3; 4-methoxycyclohexanedione-1,3;4-ethoxycyclohexanedione 1,3; 4 carbomethoxycyclohexanedione-1,3;4-carboethoxycyclohexanedione-1,3; 4-methoXy-5,5-diethylcyclohexanedione1,3;, 4-ethoxy-5,5-diethylcyclheXanedione-L3;4-carbomethoxy-5,5-diethylcyclohexanedione-lfi; 4-carboethoxy 5,5diethylcyclohexanedime-1,3; 4-n-amylcyclohexanedione-1,3 -n-amylcyclo-'hexanedione-l,3; 4,6 dibromo 5,5 dimethvlcyclohexanedime-1,3;5-(l-ethylpropyl) cyclohexanedione-L3 andS-(p-hydroxyphenyl)-cyclohexanedione-1,3 are illustrative of thecyclohexanedione-lfi compounds used in the preparation of the azocompounds of our invention. The use of5,5-dimethylcyclohexanedione-1,3yappears t'oibe advantageous. a

The non-metallized monoazo dye compounds of our invention have varyingutility for the dyeing of cellulose alkyl carboxylicacid esters havingtwo to four carbon atoms in the acid groups thereof, nylon,acrylonitrile polymers, such as polyacrylonitrile and acrylonitrilegraft polymers, and polyesters, such as polyethylene terephthalate.After application to these materials, usually in the form of textilematerials, the dye may be metallized thereon, if desired. The metallizedazo compounds of our invention can be applied by ordinary dyeing orprinting techniques to nitrogenous textile materials such ample.Coloration can also be eifected by incorporating the non-metallized ormetallized azo compounds into the spinning dope, spinning the fiber asusual and converting the non-metallized azo compounds to theirmetallized form if desired. Also the metallizing agent can beincorporated in the spinning dope, the fiber spun as usual and then dyedwith the non-metallized monoazo compounds to form the metal complex onthe fiber. The new metallized dyes of our invention are preferablyformed by heating the non-metallized azo dye with the metallizing agentin organic solvents, such as, for example, cellulose acetate, celluloseacetate-propionate, acrylonitrile polymers, polyamides, methylCellosolve and formamide.

Both the non-metallized and metallized monoazo compounds of ourinvention are dyes for fibers prepared from graft polymers obtained bygraft polymerizing acryloni-' trile alone or together with one or moreother monoethylenic monomers with a preformed polymer. The preformedpolymer can be a homopolymer (a polymer prepared by polymerization of asingle monomer) or it can be an interpolymer such as a copolymer (apolymer prepared by the simultaneous polymerization in a single reactionmixture of two monomers) or a terpolymer (a polymer prepared by thesimultaneous polymerization in a single reaction mixture of threemonomers), or the like, and the graft polymers for which the dyes areparticularly useful are those containing at least 5% by weight ofcombined acrylonitrile grafted to the preformed polymer molecule.

- The graft polymers which can be dyed using the nonmetallized andmetallized dyes are thus polymers having directed placement of thepolymerized monomeric units in the graft polymer molecule asdistinguished fromthe random distribution obtained in interpolymerswhich are,

prepared by simultaneous polymerization of all of the monomericmaterials in the polymer. The preformed polymer can be either ahomopolymer of any of the Wellknown polymerizable 'monomers' containinga single -CH=C group and desirably a CH =C group, or

an interpolymer of two or more of such monomers; and the grafting can beeffected with the preformed homopolymer or interpolymer in thepolymerization mixture in which it was formed (i. e. a live polymer) orwith the preformed polymer isolated from the polymerization mixture inwhich it was formed (i. e. a dead polymer).

The preformed polymer desirably is a homopolymer of a vinyl pyridine, anacrylamide, a maleamide, a fumar-' amide, an acrylate, a methacrylamide,a methacrylate,

an itaconamide, a citraconarnide, a fumaramate, an itaconamate, acitraconamate, a maleamate, or a vinyl ester; or an interpolymer of twoor more of such monomers with each other or of at least one of suchmonomers with one or more different monoethylenic monomers characterizedby a CH=C group such as styrene, acrylo-v acrylonitrileora mixture ofacrylonitrile with any other monoethylenic monomer, including any of themonomers enumerated hereinaboye, with the preformed live or deadvhomopolymer or interpolymer whereby the acrylonitrile alone or togetherwith another grafting monomer is com-j bined with the preformed polymermolecule to give a graft polymer containing fromv5 to by weight ofcombined acrylonitrile. a

The new azo compounds ofour invention are of particular utilityfordyeing fibers prepared from'a graft. polymer obtained by graftpolymerizing acrylonitrile andan acrylamide or methacrylamide with apreformed copolymer of acrylonitrile and the same or difierentacrylamide or methacrylamide.

U. S. Patent 2,620,324 issued December -2, 1952, U. S. Patent 2,649,434issued August 18, 1953, and U. S. Patent 2,657,191 issued October 27,1953, disclose other typical graft polymers that can be dyed with thenew no compounds of our invention. v

The following examples in which parts are expressed as parts by weightillustrate our invention.

EXAMPLE 1 50 parts of propionic-acetic (1:5 acids were added at C. to asolution of 3.8 parts of sodium nitrite in 45 parts of concentratedsulfuric acid (94%). A solution of 9.1 parts of2-amino-6-methoxybenzothiazole in 50 parts of propionic-acetic (1:5)acids was added at 5 C. to the sodium nitrite solution and the resultingreaction mixture was stirred for 2 hours at 5 C. The diazonium solutionthus obtained was added at 5 C. to a solution of 9.8 parts of4-carboethoxy-5,5-dimethylcyclohexanedione-l,3 in 150 parts ofpropionic-acetic (1:5) acids. After 2 hours stirring at roomtemperature, the reaction mixture was made neutral to Congo red paperwith ammonium acetate (sodium acetate can also be used) and then drownedin 2000 parts of cold water. The reaction product which precipitated wasrecovered by filtration, washed with cold water until neutral and driedat 60 C. under vacuum. 15.8 parts of the dye compound having theformula:

were obtained. This dye compound dyes cellulose acetate yellow shades.

EXAMPLE 2 130 parts of concentrated sulfuric acid were added at roomtemperature to a slurry of 11.4 parts of 2-amino-6-methyl-sulfonylbenzothiazole in 120 parts of water. The temperature ofthe reaction mixture rose to about 90 C. and the2-amino-6-methyl-sulfonylbenzothiazole dissolved. After cooling to -l0C., a solution of 4.2 parts of sodium nitrite in 47 parts ofconcentrated sulfuric acid was carefully added to the reaction mixturewith stirring while keeping the temperature of the reaction mixture at-5 C. or below. After stirring for 2 hours at -5 C., the diazoniumsolution resulting was added to a solution of 7.0 parts of5,5-dimethylcyclohexanedione-l,3 in 150 parts of propionic-acetic (1:5)acids at 0 C. After 2 hours stirring below 5 C., the mineral acidpresent in the reaction mixture was made neutral to Congo red paper bythe addition of sodium or ammonium acetate following which the reactionmixture was drowned in 2000 parts of cold water. The dye product whichprecipitated was recovered by filtration, washed well with cold waterand dried at 60 C. under vacuum. 13.8 parts of a dye compound which dyescellulose acetate yellowish-brown shades were obtained.

EXAMPLE 3 By the use of 9.75 parts of 2-amino-6-nitrobenzothiazole inExample 1 in place of 2-amino-6-methoxybenzothiazole 17 parts of a dyecompound which dyes cellulose acetate yellow shades were obtained.

EXAMPLE 4 A cellulose acetate dull spun fabric dyed with a 3% dyeing ofthe dye product of Example 1 was padded with a 2% aqueous solutionofnickel thiocyanate-underton (5 in Example 1 in place ofkamiuo=6-xn'ethoxybenzdthia ditions such that a 60m pick-up based on theweight of the fabric was obtained. The cellulose acetate fabric was airdried and then aged in a steam chest at 5 p. s. i. pressure for 20minutes following which it was scoured at 60 C. with soap and water,rinsed well with water and dried. By this treatment the original yellowdye fabric'was dyed a pleasing red shade. No bleeding was observed whena sample of the dyedfabric was subjected to a standard AATCC wash testat F. with soap and water. Further, while the original yellow dyeingshowed a break after 5 hours on the Fade-Ometer, the metallized dyeingshowed no fading after 20 hours exposure on the Fade-Ometer.

EXAMPLE 5 A cellulose acetate fabric dyed with a 3 dyeing of the dyeproduct of Example 2 was treated with a 2% aqueous solution of nickelthiocyanate in accordance with the procedure described in Example 4. Astriking green dyeing having excellent fastness to light and washing wasobtained.

EXAMPLE 6 A cellulose acetate fabric dyed with a 3% dyeing of the dyeproduct of Example 1 was treated with a 2% aqueous solution of ferrousthiocyanate in accordance with the procedure described in Example 4. Apleasing brown dyeing having good fastness to light and washing wasobtained EXAMPLE 7 A cellulose acetate fabric dyed with a 3% dyeing ofthe dyeprodu'ct of Example 1 was treated with a 2% aqueous solution offerric thiocyanate in accordance withthe procedure described in Example4. A pleasing brown dyeing having good fastness to light and washing wasobtained.

EXAMPLE 8 A cellulose acetate fabric dyed with a 31% dyeing of the dyeproduct of Example 2 was treated with a 2% aqueous solution of ferrousthiocyanate in accordance with the procedure described in Example .4. Apleasing brown dyeing having good fastness to light and washing wasobtained.

EXAMPLE 9 A cellulose acetate fabric dyed with a 3% dyeing of the dyeproduct of Example 2 was treated with a 2% aqueous solution of ferricthiocyanate in accordance with the procedure described in Example 4. Apleasing brown dyeing having good fastness to light and washing wasobtained. l I

EXAMPLE 10 A cellulose acetate dull spun fabric dyed wtih a 3% dyeing ofthe dye product of Example 1 was padded with a solution of 6 partsCuprofix (a mixture of copper sulfate and a low ureaformaldehyde resin)in 200 parts of water and then dried. The dried padded cellulose acetatefabric was then cured at 160 C. for 5 minutes and then scoured at 60 C.with a solution of 1 part of Calgon (sodium hexameta-phosphate) and 1part of lgepal CA (a polymerized ethylene oxide-alkyl phenolcondensation product) in 100 parts of water, rinsed with water anddried. The cellulose acetate fabric was dyed a Bordeaux shade havinggood fastness to light and washing.

EXAMPLE 11 By the use of 9.8 parts of 2-amino-6-ethoxybenzothiazole and6.47 parts of 5,S-dimethylcyclohexanedione-1,3

EXAMPLE 12 2.5 grams of the dye product of Example 11 were refluxed in50 cc. of ethylene glycol monomethyl ether with 1.5 grams of nickelousacetate crystals and 2 cc. of 28% aqueous ammonium hydroxide for 3hours. The reaction mixture was then cooled and poured into 2000 cc. ofwater containing 50 gramsof sodium chloride. The metallized dye productwhich precipitated was recovered by filtration, washed well with coldwater and dried. 2.8 grams of a red pigment were thus obtained.

EXAMPLE 13 By the use of 9.9 parts of 2-amino-6-nitrobenzothiazole and6.5 parts of 5,5-dimethylcyclohexanedione- 1,3 in Example 1 in place of2-amino-6-methoxybenzothiazole and4-carboethoxy-5,S-dimethylcyclohexanedione-1,3, respectively, a goodyield of a dye compound which dyes cellulose acetate yellow shades wasobtained.

EXAMPLE 14 EXAMPLE is By the use of 2.3 grams of chromium fluoride inplace of cobaltous chloride in Example 14 a dark brown pig ment isobtained.

EXAMPLE 16 By the use of 10.5 parts of2-amino-4,7-dimethoxybenzothiazole and 6.47 parts of5,5-dimethylcyclohexanedime-1,3 in Example 1 in place of2-amino-6-methoxybenzothiazole and4-carboethoxy-S,S-dimethylcyclohexanedione-1,3, respectively, a goodyield of a dye compound which dyes cellulose acetate yellow shades wasobtained.

EXAMPLE 17 A slurry of grams of the dye product of Example 16 in 100 cc.of ethyl alcohol was brought to the boiling point and cc. of a 20%solution of nickel thiocyanate in water was added and the resultingmixture was refluxed for 2 hours. The cooled reaction mixture was pouredinto 2000 cc. of water containing 50 grams of sodium chloride. The dyecompound which. precipitated was recovered by filtration, washed .wellwith cold water and dried. 5.9 grams of a dark brown pigment were thusobtained.

EXAMPLE 18 To a refluxing solution of 1.8 parts of the dye product ofExample. 2 in 30 cc. of acetone there. were added 4 parts of 28% aqueousammonium hydroxide followed by theaddition of a solution of 2 parts ofnickel acetate tetrahydrate in 30 parts of acetone. The reaction mixturewas refluxed with stirring for 2 hours longer and then drowned in 300parts of water. The metallized dye,cQmpoundwhichprecipitated. wasrecovered by. tiltration; washed with water and thendried under vacuat60 ,C, 1.93. parts of a metallized dye compound which, when incorporatedby known means into films, filaments, etc; of cellulose acetate, impartsgreenishgrey shades of good fastness properties thereto were ob- .tainedEXAMPLE 19 50 parts of acetic-propionic (5:1) acid were added to asolution of 3.8 parts of sodium nitrite in 46 parts of sulfuric acid(94%) at 15 C. 9.1 parts of 2-amino-6- methoxybenzothiaaole were addedto the reaction mixture at a temperature below 5 C., with stirring,following which 50 parts of acetic-propionic (5 :1) acid were alsoadded. The reaction mixture thus obtained was stirred 2 hours longer at5 C. and then added to a solution of 7 parts of5,5-dimethylcyclohexanedione-1,3 in parts of acetic-propionic (5 :1)acid below 5 C. The reaction mixture was made neutral to Congo red paper(i. e. the mineral acid is neutralized) by the addition of ammoniumacetate and stirred for 2 hours without cooling. Following this thereaction mixture was drowned in 1200 parts of water and the dye compoundwhich precipitated was recovered by filtration, washed well with waterand dried under vacuum at 60 C. 15.8 parts of a dye compound whichcolors the polyacrylonitrile graft polymers described herein richredbrown shades having good fastness to light were obtained.

EXAMPLE 20 To a refluxing solution of 1.72 parts of the dye product ofExample 19 in 30 cc. of acetone there were added 4 parts of 28% aqueousammonium hydroxide followed by the addition of a solution of 2 parts ofnickel acetate tetrahyd'rate in30 parts of acetone. The reaction mixture was refluxed with stirring for 2 hours longer and then drowned in300 parts of'water. The metallized dye compound which precipitated wasrecovered by filtration, washed with water and then dried under vacuumat 60 C. 1.78 parts of a metallized dye compound were thus obtained.When incorporated into a cellulose acetate dope solution which is thenspun into yarn, red-brown filaments having good resistance to the actionof light and laundering are obtained.

EXAMPLE 21 To a refluxing solution of 1.78 parts of the dye product ofExample 13 in 30 cc. of acetone there were added 4 parts of 28% aqueousammonium hydroxide followed by the addition of a solution of 2 parts ofnickel acetate tetrahydrate in 30 parts of acetone. The reaction mixturewas refluxed with stirring for 2 hours longer and then drowned in 300parts of water. The metallized dye compound which precipitated wasrecovered by filtration, washed with water and then dried under vacuumat 60"C. 1.81parts of a nietallized dye compound which yields rich brownshades when incorporated into cellulose acetate compositions wereobtained.

.The dye compounds of Examples 1, 2 and 3 color the acrylonitrile graftpolymer specifically described hereinafter brown, olive and" brownshades, respectively.

The following tabulation further illustrates the monoazo compounds ofour invention and sets forth the colors the non-metallized compoundsyield on (1) cellulose acetate and-(2) on an acrylonitrile graftpolymer, as well as the colors obtained on cellulose acetate when thenon metallized compounds are metallized on the fiber. The preparation ofthe acrylonitri-le graft polymer referred to in the tabulation isdescribed immediately following the tabulation; C. A." refers tocellulose acetate, Originalrefers to the non-metallized dyeing and Finalrefers to the metallized dyeing Color on CA- Color onzamlnobenzothiazole Metalllzlng Acrylonltrile Compound CouplingComponent Agent Graft Original. Final Polymer O i i4-Cy1ano-5-phenylcyelohexanedlone-lfi brown.

do 5,5%lmethylcyclohexanedione-1,3 yellow. n d0 74-Methoxy-5,5-dimethylcyclohexanedlone-1,3. brown.4-1i)agrbomethoxy-S,S-dImethylcYclohexanedlonered.4-darbethoxy-5,fi-dlmethylcyclohexanedlone-l,3. brown.

5,5-Dimethylcyclohexanedlone-1,3 Do. do D0.

D0 fl-N-llslthylsulfamldmnn Do.

0 d-fl-Hydroxyethyl Do.

Do Do Do. ])o. %o 4-C{lane-5-phenyleyclohexanedlone-l,3-. red.

0 o 6-Cyano 5,5-Dlmethylcycl0hexanedione-l,3 violet.

D dn 00(SON): .-.do grey' NKSCN): d red orange.

I Do.

brown.

- orange; orange. brown red-violetbrown. pinkallciethylcyelohexane(lions-1,3 o Cyclohexanedlone-1,3 do

do do fi-Meithylcyelohexanedlone-L3- O Ethyl 5,5dlmethylcyclohexanedlone 1,3 -earbogylateA.

Preparation of acrylonitrile graft polymer 3.0 g. of acrylonitrile and7.0 g. of N-methyl methacrylamide were emulsified in 40 cc. of watercontaining 0.15 g. of potassium persulfate and 0.01 g. of tertiarydodecyl mercaptan. The emulsion was heated at 60 C. until 94% or more ofthe monomers had copolymerized. This result is usually accomplished byheating for about l2,hours. The copolymer contained approximately 30% byweight of acrylonitrile and 70% by 'weight of N-methyl methacrylamide.The mixture wasthen cooled to room temperature, 50 cc. oi wa ter addedandth'e mixture agitated until a homogeneous solutionof dope containing10% by weight of the. copoly mer resulted. i i

30.7 g. (3.07 g. of copolymer) of theabove prepared solution or .dopeof' the copolym er were placed in a iacketed reactor provided with-anagitator andv heat exchanger. .There werethen added 10g. ofacrylonitrile, 114 cc. of water, 0.58 g. of 85% phosphoric acid, 0.1 g.of potassium persulfate, 0.17 g. ofpotassium metabisulfite, 0.1g. oftertiary dodecyl mercaptan and 0.56 g.o f a solution in water ofN-methyl methacrylamide and the. mixture heated, with stirring, to C.and then allowed to level off at -3739 C. After the heat ofpolymerization ,hadbeen removed and whenthe conversion of theacrylonitrile to polymer had reached.96% or more, which is usuallyaccomplished in a period of about 12 hours, the temperature was raisedto 90 C. The, mother liquor was removed by centrifuging thepolymerization mixture, the polymer precipitate being reslurried twicewith water and centrifuged to a 7. moisture cake. The cake was driedunder vacuum at 80? C. in an agitated dryer. The over-all yield of moditied polyacrylonitrile product was over 90%. ;After hammer-milling, thedry powder, now ready for spinning, 'was stored in a moisture proofcontainer.

The acrylonitrile graft polymer. prepared as aboveand containing about18% by weight of Nrmethyl methacrylamide was soluble inN,N-dimethylformamide. 1 Fibers spunbyextruding a. solution of the:polymer, product in -N,Ndiinethyltormamide into a precipitating bath-had'a softening temperature of about 240 C., an extensibility of about20-30 percent depending on the drafting and relaxing conditions, andshowed excellent atfinity for dyes.

In order that the preparation of the azo compounds of our invention maybe entirely clear, the preparation of certain intermediates used intheir manufacture is described hereinafter.

Preparation of Z-aminto-o-methylsulfonylbenzothiazole A solution of 200parts of bromine in 300 parts of acetic acid was added over the courseof about 1 hour to amixture of: 171 parts .of p-aminophenylmethylsulfoneand 202 parts of sodium thiocyanate in- 1750 parts of acetic acid. Thetemperature was held below 35 C. during. the. addition and aftercomplete addition; of the bromine-acetic acid mixture, the reactionmixture was stirred for 18 hours. The reaction product was recovered onthe filterby filtration, washed with acetic acid and then dispersed in6000.parts1of water. The reaction mixture thus obtained was heated 'toboiling and then an alkali such as, caustic soda or'sodium carbonatewas'added until the pH of the reaction mixture Was about 6. The reactionmixturewasthen cooled, filtered and the reaction product which collectedon the filter was washed well with wateranddried atl20 C. to parts of2-aminofi-methylsulionylbenzothiazole were obtained as1ightyellowerystalsmelting at;226. C.228: C.

Preparation of Z-acetylaming-ti-thiocyanobenzothiazole To a solution of18.6 parts of aniline and 30.4 parts of ammonium thiocyanate in 300 parts of acetic acid at C. 14.2 parts of chlorine were bubbled in at 15C.l7 C. 30 minutes after addition of the chlorine 15.6 parts of sodiumacetate and 30.4 parts of ammonium thiocyanate were added to thereaction mixture. While holding the temperature of the reaction mixturebelow 35 C.,- 14.2 parts of chlorine were passed in and the reactionmixture was stirred overnight atroom temperature. The solid present inthe reaction mixture was recovered by filtration, washed with 50 partsof acetic acid and then suspended'in to boiling and filtered. 30 partsof sodium acetate were added to the filtrate and the solid whichprecipitated was collected at 70 C. on a filter, washed with 200 partsof {f H Rreparation of Z-amino-d-isobntylsulfanylbenzothiazole.

This compound was prepared in accordance with the procedureg describedfor the preparation of 2-amino 6- ethylsulfonylbenzothiazole using 14.3parts of isobutyl bromide in place of ethyl iodide. The melting point ofthe .2-acetylamino-6-isobutylthiobenzothiazole obtained iwas'167" C.-168C. while that of the final product 2'-amiuo-6-isobutylsulfonylbenzothiazole was 2062-amino-6-n-butylsulfonylbenzothiazole is similarly prepared by using14.3 parts of n-butyl bromide in place of isobutyl bromide in theforegoing example. 600 parts of water. The mixture thus obtained washeated 15 fPreparation of Z-amino-6-trifluoromethylsulfonylbenza- V Vtltiagole V V 75 parts of brominein lZO parts of acetic acid were fadded gradually with stirring to a solution of 98 parts ofp-aminophenyltrifluoromethylsulfone and 76 parts of sodisolution of 52.6parts of the above product in 81 parts of I".

acetic acid, and the temperature of the reaction mixture was held at 80C.-90 C. for one hour. The reaction mixture was then poured into 1000parts of cold water and the product which precipitated was recovered byfiltration, washed with 500 parts of water and then dried at 60 C. 62parts of 2-acetylamino-6-thiocyanobenzothiazole melting at 247 C.249 C.were thus obtained.

Preparation of 2-amin0-6-ethylsulfonylbenzothiazole A solution of 26.4parts of crystalline sodium sulfide-and I 24.9 parts of 2acetylamino-6-thiocyanobenzothiazole in 150 parts of ethyl alcohol wererefluxed together for 10 minutes and after cooling the reaction mixtureto 20 C.,

jum thiocyanate in 700 parts of acetic acid. The addition of the brominewas begun at room temperature and the for 24 hours at room temperaturefollowing which it was poured into 5000 parts of cold water and themineral acid therein neutralized by the addition of sodium acetate with7 .good stirring.

The product which formed was recovered by filtration, washed well withcold water and dried at 16.3 parts of ethyl iodide were added at onetime and the added dropwrse, with stirring, to a solution of 12.4 partsof p-aminobenzotrifiuoride and 12.7 parts of sodium thioreaction mixtureresulting was refluxed for one hour. The reaction mixture was thenpoured into 1000 parts of water and the product which precipitated wasrecovered by filtration, washed well with water and dried at 60 C. 23.6parts of 2-acetylamino-fi-ethylthiobenzothiazole melting at 168 C.l69 C.were obtained. If desired, the quality of the product can be checked byhydrolyzing a little of the product with acid to2-amino-6-ethylthiobenzothiazole melting at 137 C.-139 C.

19 parts of aqueous hydrogen peroxide were added to a solution of 15.5parts of Z-acetylamino-6-ethylthiw beuzothiazole in 53 parts of aceticacid while maintaining the temperature of the reaction mixture between80 C.- 90 C. The reaction mixture was maintained at this temperature forone hour and then poured into 500 parts of cold water. The solid presentin the reaction mixture was recovered by filtration and then suspendedin a mixture of 800 parts of water and 100 parts of concentratedhydrochloric acid. The reaction mixture :thus obtained was heated toboiling and then filtered. The filtrate was neutralized with sodiumacetate, cooled to 25 C. and filtered. The product collected on thefilter was washedwith cold water and dried at 60 C. 8.5 parts of2-amino-6- ethylsulfonylbenzothiazole melting at 173 C.-175 C. were thusobtained.

Preparation of 2-amino-6-isopropylsulfonylbenzothiazole f C. "33 to 70parts of 2-amino-fi-trifiuoromethylsultonylbenzothiazole melting at206-208 C. were thus obtained.

ff Preparation of 2-amino-6-trifluoromethylbenzothiazale 12.5 parts ofbromine in 20 parts of acetic acid were cyanate in parts of acetic acidwhile maintaining the Preparation of2-amino-6-fi-hydr0xyethylbenzothiazole 255.7 grams of bromine in 400 cc.of acetic acid were added gradually over a period of 1 hour with goodstirring to a solution of 219.2 grams of p-aminophenylethyl alcohol and259.2 grams of sodium .thiocyanate in 2400 cc. of acetic, acid whilemaintaining the temperature of the reaction mixture below 15 C. Thereaction mixture resulting was stirred for 2 hours at 10 C.12 C. and theproduct which formed was recovered on the filter by filtration andwashed with 300 cc. of acetic acid. The product filter cake thusobtained was. dissolved in 1600 cc. of water'at about 40 C. and thereaction mixture was made alkaline bythe addition of sodium hydroxide.The reac tion mixture thus obtained was. heated to boiling and thencooled to 15 vC. and filtered. The product obtained on the filter; waswashed with water until neutral and then dried at 100 C. 206 to 230grams of 2-amino-6-phydroxyethylbenzothiazole were thus obtained in theform of white crystals melting at C.-177 C.

' Another alkali metal thiocyanate such as potassium thiocyanate, forexample, can be used in place of sodium thiocyanate in the foregoingexamples. Similarly, another alkaline agent, such as sodium carbonate,sodium bicarbonate, potassium carbonate; potassium bicarbonate, ammoniumacetate or potassium acetate, for example, can

be used to neutralize the mineral acid in place'of sodium acetate.

The preparation of p-aminophenyltrifiuoromethylsulfone is described inBritish Patent 485,592.

The non-metallized monoazo dye compounds of our invention can be appliedto cellulose alkyl carboxylic acid esters having 2 to 4 carbon atomsinthe acid groups thereof, nylon, an acrylonitrile polymer, such aspolyacrylonitrile and acrylonitrile graft polymers, and polyester, suchas polyethylene terephthalate, textile materials and the metallized azodye compounds'of our invention can be applied to nitrogenous textilematerials such as, for example, wool, silk, nylon and acrylonitrilepolymers, such as polyacrylonitrile and acrylonitrile graft polymers, inthe form of an aqueous dispersion and are ordinarily so applied.

To illustrate, the dye compound is finely ground with a dispersing agentsuch as sodium lignin sulfonate, Turkey red oil, soap, or an oleylglyceryl sulfate and the resulting mixture is dispersed in water. Thedye bath thus prepared is heated to a temperature approximating 45 C.55C. and the textile material to be dyed is immersed in the dyebath,following which the temperature is gradually raised to 80 C.-90 C. andmaintained at this temperature until dyeing is complete, usuallyone-half to two hours. From time to time throughout the dyeingoperation, the material is worked to promote even dyeing. Uponcompletion of the dyeing operation, the textile material is removed fromthe dye bath, washed with an aqueous soap solution, rinsed well withwater and dried. In the case of certain of the acrylonitrile graftpolymers described hereinbefore it is necessary to dye at the boil foran extended period of time. Instances may be encountered where the fiberis not satisfactorily colored by the dyeing procedure just described. Inthese instances special dyeing techniques, such as the use of pressure,for example, developed by the art for the coloration of materialsdifficult to color may be employed.

Widely varying amounts of dye can be used in the dyeing operation. Theamount of dye used can be, for example, /s to 3% (by weight) of that ofthe textile material although lesser or greater amounts of the dye canbe employed.

The following example illustrates one satisfactory way in which thefibers of the acrylonitrile graft polymers can be dyed using either thenon-metallized or metallized azo compounds of our invention. 16milligrams of dye are ground with an aqueous solution of sodium ligninsulfonate until well dispersed or alternately the dye can be dissolvedin cc. of hot Cellosolve. The dispersion or solution, as the case maybe, is then poured into 150 cc. of water to which a small amount of asurface-active agent such as Igepon T (C H .CO.N(CH ).C H SO Na), NekalBX (sodium alkylnaphthalenesulfonate) or Orvus (sodium laurylsulfate-type) has been added. The dye bath is then brought to thedesired temperature and 5 grams of well wet-out fibers of the graftpolymer are added thereto. Dyeing is continued until the proper shade isreached. From time to time throughout the dyeing operation, the materialis worked to promote even dyeing.

The expression propionic-acetic (1:5) acids refers to a mixture ofpropionic and acetic acids in which there are five parts by volume ofacetic acid to 1 part by volume of propionic acid.

The non-metallized azo compounds dye nylon substantially the same shadesas they dye acrylonitrile polymers.

Acrylonitrile graft polymers including those of the type specificallydescribed hereinbefore are described and claimed in Coover U. S.application Serial No. 408,012, filed February 3, 1954.2-amino-6-trifluoromethylsulfonylbenzothiazole is described and claimedby Straley and Fisher U. S. application Serial No. 4l3,954, filed March3, 1954, now abandoned. 2-amino-6-trifluoromethylbenzothiazole isdescribed and claimed by Straley i 14 and. Fisher U. S. applicationSerial No. 413,955, filed March 3, 1954, now abandoned. T v T We claim:

1. A complex metal compound which contains one of the metals selectedfrom'the group consisting" of. chromium, cobalt, copper, iron,manganese, nickel and vanadium in complex combination with a monoazocompound having the formula: i

wherein Ar represents an ortho-arylene radical of the benzene seriesdevoid of a sulfonic' acid group and X represents the radical of acyclohexanedione-L3 compound joined through the carbon atom inits2-position to the azo bond shown.

2. A complex metal compound which contains one of the metals selectedfrom the group consisting of chromium, cobalt, copper, iron, manganese,nickel and vanadium in complex combination with a monoazo compoundhaving the formula:

wherein Ar represents an ortho-arylene radical of the benzene seriesdevoid of a sulfonic acid group.

4. Complex nickel compounds of the monoazo compounds having the formulaset forth in claim 1.

5. Complex cobalt compounds of the monoazo com-- pounds having theformula set forth in claim 1.

6. A complex nickel compound of the azo compound having the formula:

7. A complex nickel compound of the azo compound having the formula:

I :1 8. A complex nickel cotnpound of the 320 compound having theformula:

9. A complex nickel compound of the azo compound 10 having the formula:

w1 Referrences Cited in the file of this patent UNITED STATES PATENTS IMcNally et a1. Oct. 1, 1940 Argyle et a1. May 18, 1948 T Bestehorn July10, 1951 Riat et a1 Apr. 29, 1952 Menzi et a1. Dec. 15, 1953

1. A COMPLEX METAL COMPOUND WHICH CONTAINS ONE OF THE METALS SELECTEDFROM THE GROUP CONSISTING OF CHROMIUM, COBALT, COPPER, IRON, MANGANESE,NICKEL AND VANADIUM IN COMPLEX COMBINATION WITH A MONOAZO COMPOUNDHAVING THE FORMULA: